WO2016080027A1 - Procédé de fabrication de capteur de détection de déplacement pour batterie secondaire de type scellé - Google Patents

Procédé de fabrication de capteur de détection de déplacement pour batterie secondaire de type scellé Download PDF

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Publication number
WO2016080027A1
WO2016080027A1 PCT/JP2015/072029 JP2015072029W WO2016080027A1 WO 2016080027 A1 WO2016080027 A1 WO 2016080027A1 JP 2015072029 W JP2015072029 W JP 2015072029W WO 2016080027 A1 WO2016080027 A1 WO 2016080027A1
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Prior art keywords
polymer matrix
secondary battery
matrix layer
container
filler
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PCT/JP2015/072029
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English (en)
Japanese (ja)
Inventor
福田　武司
敏晃 河合
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東洋ゴム工業株式会社
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Application filed by 東洋ゴム工業株式会社 filed Critical 東洋ゴム工業株式会社
Priority to KR1020177012527A priority Critical patent/KR20170070112A/ko
Priority to US15/510,759 priority patent/US20170276735A1/en
Priority to CN201580048089.1A priority patent/CN106716052A/zh
Publication of WO2016080027A1 publication Critical patent/WO2016080027A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/392—Determining battery ageing or deterioration, e.g. state of health
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G01B7/24—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in magnetic properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4285—Testing apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H01M10/482—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for several batteries or cells simultaneously or sequentially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0008—Magnetic or paramagnetic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • Such a secondary battery has a problem that when the electrolytic solution is decomposed due to overcharge or the like, the unit cell expands as the internal pressure increases due to the decomposition gas, and the secondary battery is deformed. In that case, if the charging current or discharging current is not stopped, it will ignite and the secondary battery will burst as the worst result. Therefore, in order to prevent the secondary battery from bursting, it is important to detect the deformation of the secondary battery due to the swelling of the single cell with high sensitivity so that the charging current and the discharging current can be stopped in a timely manner.
  • Patent Document 2 describes an internal pressure detection system in which a pressure-sensitive conductive rubber whose resistance value changes continuously is arranged inside a battery case.
  • a pressure-sensitive conductive rubber whose resistance value changes continuously is arranged inside a battery case.
  • wiring in order to detect a resistance change, wiring must be taken out of the sealed battery, and there is a concern that the sealing performance is deteriorated.
  • the deformation detection sensor of the secondary battery in addition to being required to be miniaturized so as not to compress the volume of the secondary battery, it is mounted in an arbitrary shape such as an empty volume part in the secondary battery. There is a need to. For this reason, the fact is that it is required in the market to manufacture a deformation detection sensor having excellent characteristic stability in an arbitrary shape.
  • the polymer matrix layer is mounted so as to be sandwiched between, for example, the cells adjacent to each other, between the cell and the housing that houses the cells.
  • the battery module is sandwiched between the battery module housing included in the battery pack and the battery module housing adjacent to the battery module housing, and further, in the gap between the battery module housing and the battery pack housing. Is done.
  • the polymer matrix layer may be attached in a compressed state.
  • the polymer matrix layer includes a first step of preparing a mixed solution by mixing a filler with a polymer matrix precursor, a second step of injecting the mixed solution into a container having a predetermined shape, and a polymer matrix precursor in the container. Is heated and cured to produce at least a production step including a third step of producing a polymer matrix layer integrated with the container.
  • the production method according to the present invention since the polymer matrix layer is produced in a container having a predetermined shape, the production method according to the present invention has a polymer matrix layer having a desired shape corresponding to the location of the inside and outside of the sealed secondary battery. It is possible to manufacture a deformation detection sensor for a sealed secondary battery comprising:
  • the polymer matrix layer contains a magnetic filler as the filler, and the detection unit detects a change in the magnetic field as the external field.
  • the third step includes a magnetization step of magnetizing the magnetic filler after the polymer matrix precursor in the container is heated and cured. According to this configuration, it is possible to detect a change in the magnetic field accompanying the deformation of the polymer matrix layer without wiring.
  • a Hall element having a wide sensitivity region can be used as the detection unit, a deformation detection sensor capable of highly sensitive detection over a wider range can be manufactured.
  • the container is made of a sealing material.
  • the electrolytic solution in the sealed secondary battery is decomposed due to overcharge or the like, it may leak out of the battery and come into contact with the deformation detection sensor.
  • the polymer matrix layer of the deformation detection sensor is deformed or damaged by being attacked by the electrolyte, it may be difficult to accurately detect the deformation of the secondary battery.
  • the shape of the container is preferably the same or longer than the length (a) of the upper surface compared to the length (b) of the lower surface. It is preferable that ⁇ (a) / (b) ⁇ 2.
  • the liquid mixture is not injected into the container without generating an air pocket, etc., and it is produced depending on the size of the air pool. In some cases, defects occur in the polymer matrix layer, and as a result, the sensor function may not be sufficiently exhibited.
  • a deformation detection sensor is attached to the sealed secondary battery, and the deformation detection sensor includes a polymer matrix layer 3 and a detection unit 4.
  • the detection part 4 is affixed on the surface (outer surface of an exterior body) of the cell 2, and an adhesive agent and an adhesive tape are used for the affixing as needed.
  • the polymer matrix layer 3 is formed in a container having a predetermined shape, for example, in the form of a sheet.
  • the polymer matrix layer 3 is formed in a gap in the secondary battery, for example, in a gap between adjacent single cells 2 or a single cell as shown in FIG. 2 and the housing 11 for housing it.
  • the polymer matrix layer 3 can be bent and attached to the corners of the unit cell 2 or the casing 11.
  • the polymer matrix layer 3 contains dispersed fillers that change the external field according to the deformation of the polymer matrix layer 3.
  • the detection unit 4 detects a change in the external field.
  • the detection unit 4 is disposed away from the polymer matrix layer 3 to the extent that changes in the external field can be detected, and is preferably affixed to a relatively firm location that is not easily affected by the swelling of the unit cell 2.
  • the detection unit 4 is affixed to the outer surface of the casing 11, but the present invention is not limited thereto, and the detection unit 4 may be affixed to the inner surface of the casing 11 or the casing of the battery pack.
  • These cases are formed of, for example, metal or plastic, and a laminate film may be used for the case of the battery module.
  • one polymer matrix layer 3 and one detection unit 4 are shown, but a plurality of them may be used depending on various conditions such as the shape and size of the secondary battery. Good. At that time, the polymer matrix layer 3 attached as shown in FIG. 2 and the polymer matrix layer 3 attached as shown in FIG. 3 may coexist. Further, a plurality of polymer matrix layers 3 may be attached to the same unit cell 2, or a plurality of detectors 4 may be configured to detect changes in the external field due to deformation of the same polymer matrix layer 3. Good.
  • thermosetting elastomer examples include polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, polychloroprene rubber, nitrile rubber, diene synthetic rubber such as ethylene-propylene rubber, ethylene-propylene rubber, butyl rubber, acrylic rubber, Non-diene synthetic rubbers such as polyurethane rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, and natural rubber can be mentioned.
  • a thermosetting elastomer is preferable because it can suppress the sag of the magnetic elastomer accompanying heat generation and overload of the battery. More preferred is polyurethane rubber (also referred to as polyurethane elastomer) or silicone rubber (also referred to as silicone elastomer).
  • Polyester polycarbonate polyol reacted with dicarboxylic acid, esterification of polyhydroxyl compound and aryl carbonate High molecular weight polyol polycarbonate polyols obtained by the reaction can be mentioned. These may be used alone or in combination of two or more.
  • Preferred active hydrogen-containing compounds are polytetramethylene glycol, polypropylene glycol, a copolymer of propylene oxide and ethylene oxide, 3-methyl-1,5-pentane adipate, more preferably a copolymer of polypropylene glycol, propylene oxide and ethylene oxide. It is a coalescence.
  • NCO index is preferably 0.3 to 1.2, more preferably 0.35 to 1.1, and still more preferably 0.4 to 1.05.
  • NCO index is smaller than 0.3, the magnetic elastomer tends to be insufficiently cured.
  • NCO index is larger than 1.2, the elastic modulus increases and the sensor sensitivity tends to decrease.
  • the amount of the magnetic filler in the magnetic elastomer is preferably 1 to 2000 parts by weight, more preferably 5 to 1500 parts by weight with respect to 100 parts by weight of the elastomer component. If it is less than 1 part by weight, it tends to be difficult to detect a change in the magnetic field, and if it exceeds 450 parts by weight, the magnetic elastomer itself may become brittle.
  • the liquid mixture obtained in the first step is poured into a container having a predetermined shape (second step).
  • the inside of the container may be completely filled with the mixed solution, and finally the inside of the container may be completely composed of the polymer matrix layer. May be composed of a polymer matrix layer and a void layer.
  • the mixed liquid obtained in the first step is a mixed liquid obtained by mixing a magnetic filler with a polymer matrix precursor containing an active hydrogen-containing compound and an isocyanate component, and the container is a sealing material. A configured example will be described.
  • the polymer matrix layer provided in the deformation detection sensor of the sealed secondary battery is manufactured in a sealing material having a predetermined shape
  • the polymer matrix layer can be manufactured in a desired shape, and the polymer matrix layer (that is, This is preferable because the resistance to electrolyte solution of the deformation detection sensor) can be improved.
  • thermoplastic resin examples include styrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, polyisoprene-based thermoplastic elastomers, Fluorine-based thermoplastic elastomer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, fluororesin, polyamide, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polybutadiene Etc.
  • thermoplastic resin examples include styrene-based thermoplastic elastomers, polyolefin-based thermoplastic elasto
  • thermosetting resin examples include polyisoprene rubber, polybutadiene rubber, styrene / butadiene rubber, polychloroprene rubber, diene-based synthetic rubber such as acrylonitrile / butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, butyl rubber, Non-diene rubbers such as acrylic rubber, polyurethane rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, natural rubber, polyurethane resin, silicone resin, epoxy resin and the like can be mentioned.
  • a film-like material can be suitably used. These films may be laminated, or may be a film including a metal foil such as an aluminum foil or a metal vapor deposition film in which a metal is vapor deposited on the film.
  • the container may adopt any shape according to the sealed secondary battery to be disposed, but for example, as shown in FIG. 4, the upper surface length (a) is the same as the lower surface length (b). Or it is preferable that it is long.
  • the container 5 has a shape in which the length (a) of the upper surface is the same or longer than the length (b) of the lower surface in a cross-sectional view, and 1 ⁇ (a) / (b ) ⁇ 2 is more preferable.
  • the opening of the container 5 may be sealed with the same material as the container 5, for example, a sealing material, before the polymer matrix precursor is cured.
  • the opening of the container 5 may be sealed after the polymer matrix precursor is cured.
  • the timing for sealing the opening of the container 5 may be before or after magnetizing the magnetic filler.
  • the magnetic filler in the polymer matrix layer may be uniformly dispersed or unevenly distributed.
  • the filler after introducing the filler into the elastomer component, it can be allowed to stand at room temperature or at a predetermined temperature, and then spontaneously settled according to the weight of the filler, by changing the temperature and time of standing.
  • the filler uneven distribution rate can be adjusted.
  • the filler may be unevenly distributed using a physical force such as centrifugal force or magnetic force.
  • the filler uneven distribution rate in a region where the filler concentration is high in one polymer matrix layer is preferably more than 50, more preferably 55 or more, and further preferably 60 or more.
  • the filler uneven distribution ratio in the region where the filler concentration is low is less than 50.
  • the filler uneven distribution rate in a region with a high filler concentration is 100 at the maximum, and the filler uneven distribution rate in a region with a low filler concentration is 0 at a minimum.
  • the polymer matrix layer may be composed of, for example, a polymer matrix layer having a laminated structure of two sheets. In this case, a polymer matrix layer having a high filler concentration and a polymer matrix layer having a low filler concentration are laminated. Alternatively, a polymer matrix layer containing no filler and a polymer matrix layer containing a filler may be laminated.
  • a known catalyst can be used without limitation, but triethylenediamine (1,4-diazabicyclo [2,2,2] octane), N, N, N ′, N ′.
  • -Tertiary amine catalysts such as tetramethylhexanediamine and bis (2-dimethylaminoethyl) ether, and metal catalysts such as tin octylate, lead octylate, zinc octylate, and bismuth octylate can be used. These may be used alone or in combination of two or more.
  • the foam stabilizer used for the polyurethane resin foam for example, a silicone foam stabilizer, a fluorine foam stabilizer, or the like used in the production of a normal polyurethane resin foam can be used.
  • the silicone-based surfactant and fluorine-based surfactant used as the silicone-based foam stabilizer and the fluorine-based foam stabilizer have a polyurethane-soluble part and an insoluble part in the molecule.
  • the insoluble part uniformly disperses the polyurethane material and lowers the surface tension of the polyurethane system, so that bubbles are easily generated and are hard to break. Of course, if the surface tension is too low, bubbles are not easily generated.
  • the dimethylpolysiloxane structure as the insoluble part can reduce the cell diameter or increase the number of cells. Become.
  • silicone foam stabilizers examples include “SF-2962,” “SRX 274DL,” “SF-2965,” “SF-2904,” “SF-2908,” manufactured by Toray Dow Corning, "SF-2904", “L5340”, Evonik Degussa AG of “Tegosutabu (Tegostab R) B8017, B- 8465, B-8443 “ and the like.
  • SF-2904" SRX 274DL
  • SF-2965 SF-2904
  • SF-2908 manufactured by Toray Dow Corning
  • the blending amount of the foam stabilizer is preferably 1 to 15 parts by mass, more preferably 2 to 12 parts by mass with respect to 100 parts by mass of the resin component. If the blending amount of the foam stabilizer is less than 1 part by mass, foaming is not sufficient, and if it exceeds 15 parts by mass, bleeding may occur.
  • the foam content of the foam forming the polymer matrix layer 3 is preferably 20 to 80% by volume.
  • the bubble content is 20% by volume or more, the polymer matrix layer 3 is flexible and easily deformed, and the sensor sensitivity can be improved satisfactorily. Further, when the bubble content is 80% by volume or less, embrittlement of the polymer matrix layer 3 is suppressed, and handling properties and stability are improved.
  • the bubble content is calculated based on the specific gravity measured according to JIS Z-8807-1976 and the specific gravity value of the non-foamed material.
  • the average cell diameter of the foam forming the polymer matrix layer 3 is preferably 50 to 300 ⁇ m.
  • the average opening diameter of the foam is preferably 15 to 100 ⁇ m.
  • the stability of the sensor characteristics tends to deteriorate due to an increase in the amount of the foam stabilizer.
  • the average bubble diameter exceeds 300 ⁇ m or the average opening diameter exceeds 100 ⁇ m, the contact area with a single cell to be detected tends to decrease and stability tends to decrease.
  • the average bubble diameter and the average opening diameter are determined by observing the cross section of the polymer matrix layer with a SEM at a magnification of 60 times, and using the image analysis software for the obtained image, all the bubbles present in the arbitrary range of the cross section. The bubble diameter and the opening diameter of all open bubbles are measured and calculated from the average value.
  • the closed cell ratio of the foam forming the polymer matrix layer 3 is preferably 5 to 70%. Thereby, excellent stability can be exhibited while ensuring ease of compression of the polymer matrix layer 3.
  • the volume fraction of the filler with respect to the foam forming the polymer matrix layer 3 is preferably 1 to 30% by volume.
  • the polyurethane resin foam described above can be produced by an ordinary method for producing a polyurethane resin foam except that it contains a magnetic filler.
  • the method for producing a polyurethane resin foam containing the magnetic filler includes, for example, the following steps (i) to (v).
  • a chemical foaming method using a reactive foaming agent such as water is known.
  • an isocyanate group-containing urethane prepolymer such as steps (ii) and (iii) described above.
  • a mechanical foaming method in which a mixture containing a foaming agent, a catalyst and a magnetic filler and an active hydrogen component are mechanically stirred in a non-reactive gas atmosphere.
  • the molding operation is simpler than the chemical foaming method, and water is not used as the foaming agent. Therefore, the molded product has tough and excellent resilience (restorability) with fine bubbles. Is obtained.
  • an isocyanate group-containing urethane prepolymer is formed from a polyisocyanate component and an active hydrogen component as in the step (i), and an isocyanate group-containing urethane prepolymer and a foam stabilizer as in the primary stirring step (ii). Then, the catalyst and the magnetic filler are mixed, pre-stirred, and vigorously stirred so as to take in bubbles in a non-reactive gas atmosphere, and the active hydrogen component is further added as in the secondary stirring step (iii). Stir vigorously to prepare a cell-dispersed urethane composition containing a magnetic filler.
  • a method for forming a polyurethane resin foam after previously forming an isocyanate group-containing urethane prepolymer is as follows: It is known to those skilled in the art, and the production conditions can be appropriately selected depending on the compounding material.
  • the blending ratio of the polyisocyanate component and the active hydrogen component is the ratio of the isocyanate group in the polyisocyanate component to the active hydrogen group in the active hydrogen component (isocyanate group / active hydrogen).
  • the group) is selected to be 1.5 to 5, preferably 1.7 to 2.3.
  • the reaction temperature is preferably 60 to 120 ° C., and the reaction time is preferably 3 to 8 hours.
  • conventionally known urethanization catalysts and organic catalysts such as lead octylate marketed by Toei Chemical Co., Ltd.
  • any apparatus can be used as long as it can react by stirring and mixing the above materials under the above-described conditions, and an apparatus used for ordinary polyurethane production can be used. it can.
  • a method using a general mixer capable of mixing a liquid resin and a filler can be used, and examples thereof include a homogenizer, a dissolver, and a planetary mixer.
  • the foam stabilizer is added to the isocyanate group-containing urethane prepolymer side and stirred (primary stirring), and in the step (iii), the active hydrogen component is further added and the secondary stirring is performed. It is preferable because bubbles taken into the reaction system are difficult to escape and efficient foaming can be performed.
  • the non-reactive gas in the step (ii) is preferably a non-flammable gas, and specifically, nitrogen, oxygen, carbon dioxide gas, helium, argon and other rare gases, and mixed gases thereof are exemplified, and dried to moisture. It is most preferable to use air from which air is removed.
  • the conditions for the primary stirring and the secondary stirring, particularly the primary stirring can be used at the time of urethane foam production by a normal mechanical foaming method, and are not particularly limited. Using a mixer, vigorously stir for 1 to 30 minutes at a rotational speed of 1000 to 10000 rpm. Examples of such an apparatus include a homogenizer, a dissolver, and a mechanical floss foaming machine.
  • the curing conditions are not particularly limited, and preferably from 60 to 200 ° C. for 10 minutes to 24 hours. If the curing temperature is too high, the resin foam is thermally deteriorated and mechanical strength is deteriorated. If the curing temperature is too low, curing failure of the resin foam will occur. On the other hand, if the curing time is too long, the resin foam is thermally deteriorated and mechanical strength is deteriorated. If the curing time is too short, the resin foam is poorly cured.
  • the polymer matrix layer may contain conductive fillers such as metal particles, carbon black, and carbon nanotubes as fillers, and the detector may detect changes in the electric field (resistance or change in dielectric constant) as an external field. It is done.
  • Polyol A Polyoxypropylene glycol obtained by adding propylene oxide to glycerol as an initiator, OHV56, functional group number 3 (Asahi Glass Co., Ltd., EX-3030)
  • Bismuth octylate Pucat 25 (Nippon Chemical Industry Co., Ltd.)
  • This filler dispersion was degassed under reduced pressure, and 100.0 parts by weight of the above prepolymer A, which had been degassed under reduced pressure in the same manner, was added, mixed and defoamed with a rotation / revolution mixer (Sinky Corp.), and the magnetic filler was removed.
  • a contained polyurethane composition (polymer matrix precursor) was prepared.
  • Examples 3 to 6 A magnetic polyurethane resin was obtained in the same manner as in Example 1 except that the upper surface / lower surface ratio of the polyethylene container was changed.
  • Magnetic flux density change A Hall element (EQ-430L, manufactured by Asahi Kasei Electronics Co., Ltd.) as a detection unit was attached to a stainless steel plate with a double-sided tape.
  • the magnetic polyurethane resin produced from this upper surface was affixed, a pressure was applied using a 50 mm ⁇ 50 mm surface indenter, and the change in magnetic flux density when no pressure was applied at the time of 10% strain (at the time of 0% strain) was measured.
  • the magnetic polyurethane resin according to Comparative Example 1 was obtained by inserting a cured elastomer into a container, resulting in positional displacement due to vibration and very poor characteristic stability.
  • the container-integrated magnetic polyurethane resins according to Examples 1 to 6 have a sufficiently large change in magnetic flux density and excellent property stability.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Secondary Cells (AREA)
  • Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
  • Battery Mounting, Suspending (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un capteur de détection de déplacement qui est destiné à une batterie secondaire de type scellé et est pourvu d'une couche de matrice de polymère qui comprend une charge dispersée qui modifie un champ externe en réponse au déplacement de la couche de matrice de polymère, et une unité de détection, qui détecte un changement du champ externe, le procédé comprenant une première étape de préparation d'un mélange par mélange de la charge avec un précurseur de matrice de polymère, une deuxième étape d'injection du mélange dans un récipient ayant une forme prescrite, et une troisième étape pour produire une couche de matrice de polymère qui est intégrée avec le récipient par chauffage et durcissement du précurseur de matrice de polymère dans le récipient.
PCT/JP2015/072029 2014-11-20 2015-08-04 Procédé de fabrication de capteur de détection de déplacement pour batterie secondaire de type scellé WO2016080027A1 (fr)

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KR1020177012527A KR20170070112A (ko) 2014-11-20 2015-08-04 밀폐형 2차 전지의 변형 검출 센서의 제조 방법
US15/510,759 US20170276735A1 (en) 2014-11-20 2015-08-04 Method for manufacturing displacement detection sensor for sealed-type secondary battery
CN201580048089.1A CN106716052A (zh) 2014-11-20 2015-08-04 密闭型二次电池的变形检测传感器的制造方法

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JP2014235473A JP2016099193A (ja) 2014-11-20 2014-11-20 密閉型二次電池の変形検出センサの製造方法
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TWI697019B (zh) * 2018-06-11 2020-06-21 海華科技股份有限公司 支架、光學組件及光學模組
TWI681424B (zh) * 2018-06-11 2020-01-01 海華科技股份有限公司 光學元件、光學組件及光學模組
KR20240024694A (ko) * 2022-08-17 2024-02-26 주식회사 엘지에너지솔루션 배터리 제조 공정 관리 시스템 및 이의 동작 방법

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JP2009076265A (ja) * 2007-09-19 2009-04-09 Panasonic Corp 電池パック
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TWI556492B (zh) 2016-11-01
TW201620196A (zh) 2016-06-01

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